Cesium carbonate → 2'-Methyl-4'-nitro-biphenyl-3-sulfinic acid methyl ester

HRID 132080Notes

Reaction equation

HRID 132080 reaction equation
[CH3:1][S:2]([OH:4])=[O:3].Br[C:6]1[CH:7]=[CH:8]C=[CH:10][CH:11]=1.CC1(C)C(C)(C)OB([C:20]2[CH:25]=[CH:24][C:23]([N+:26]([O-:28])=[O:27])=[CH:22][C:21]=2[CH3:29])O1.[C:31](=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:31][O:3][S:2]([C:1]1[CH:10]=[C:11]([C:20]2[CH:25]=[CH:24][C:23]([N+:26]([O-:28])=[O:27])=[CH:22][C:21]=2[CH3:29])[CH:6]=[CH:7][CH:8]=1)=[O:4]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 248204924,4,5,5-Tetramethyl-2-(2-methyl-4-nitrophenyl)-1,3,2-dioxaborolaneHCID 866115163-Bromobenzene methyl sulfinate

Product 1

HCID 597336502'-Methyl-4'-nitro-biphenyl-3-sulfinic acid methyl esterYield 56%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolvent

Procedure

A solution of 3-bromobenzene methyl sulfinate (541 mg, 2.3 mmol), 4,4,5,5-tetramethyl-2-(2-methyl-4-nitro-phenyl)-[1,3,2]dioxaborolane (484 mg, 1.84 mmol), cesium carbonate (900 mg, 2.76 mmol), and Pd(dppf)Cl2 (145 mg, 0.18 mmol) was stirred in DMF at 80° C. for 4 h under argon. The mixture was partitioned between EtOAc (100 mL) and aq NH4Cl (30 mL) and the layers were separated. The organic layer was further washed with water (4×30 mL), brine (30 mL), and was dried over Na2SO4. Concentration of the solution followed by purification of the residue via silica gel chromatography (2-10% EtOAc in hexanes) yielded the product as a colorless oil (300 mg, 56%). 1H NMR (CDCl3): δ 8.19 (m, 1H), 8.12 (ddd, 1H, J=0.6, 2.5, 8.4 Hz), 7.77 (ddd, 1H, J=1.2, 1.8, 7.8 Hz), 7.65-7.71 (m, 2H), 7.54 (ddd, 1H, J=1.2, 1.8, 7.6 Hz), 7.41 (d, 1H, J=8.4 Hz), 6.65 (s, 1H), 3.58 (s, 3H), 2.38 (s, 3H).

Workup

  1. customThe mixture was partitioned between EtOAc (100 mL) and aq NH4Cl (30 mL)
  2. customthe layers were separated
  3. washThe organic layer was further washed with water (4×30 mL), brine (30 mL)
  4. dry with materialwas dried over Na2SO4
  5. customConcentration of the solution followed by purification of the residue via silica gel chromatography (2-10% EtOAc in hexanes)

Sources & evidence

ORD record
ord-545fc052dc794e6b9fe73e6371b66590
Source dataset
uspto-grants-2008_06
Patent number
US07385066B2

Reaction notes

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